Surface-active formals



SURFACE-ACTIVE FORMALS Peter L. de Benneville and Homer J. Sims,Philadelphia, Pa., assignors to Rohm & Haas Company, Philadelphia, Pa.,a corporation of Delaware No Drawing. Application September 24, 1957Serial No. 685,798

6 Claims. (Cl. 260-4105) The present invention concerns specificsymmetrical surface-active formals. It is further concerned withspecific surface-active formals that are stable under alkaline orneutral conditions but which may be altered by acidic condtions. Thisalteration may take the form of changing an oil-soluble, surface-activecompound to one of no surface activity or a water-soluble, surfaceactivecompound to one of no surface activity. This invention also concerns amethod for the preparation of the specific surface-active acetals andformals.

A wide variety of non-ionic surface-active agents is known in the art;and usually these are stable in acid, basic, and neutral media. In manyapplications it is necessary or at least highly desirable to remove orchange the surface activity of an agent at some critical point in theoperation. For example, if an ordinary non-ionic, surface-active agentis used to remove oils and waxes from raw wool by emulsification, thereis obtained an emulsion in water which is not easily broken, either forthe recovery of the oils and waxes or purposes of disposal. Also, theeflluent from commercial laundries using nonionic detergents remainshighly surface active, causing many troublesome problems of foaming anddisposal. Further, when non-ionic, surface-active agents are used forthe recovery of petroleum, there is obtained an emulsion which is noteasily broken without the use of certain complex and expensivedemulsifying agents. The present compounds can be used in all of theabove situations by employing a step in which the objectionableemulsions are treated with dilute acids which, since there is analteration in the surface-active properties of the present compounds,permits the ready and effective conclusion of the operations describedheretofore. The subject compounds may also be used in the preparation ofemulsion polymers which can well be coagulated, if desired, in fiberform by treatment with dilute acids. These compounds are easily preparedfrom only two readily available starting materials, a chloromethyl esterof a specific carboxylic acid and a polyethylene glycol. Aqueous 0.1%solutions of them display low surface tensions and good surface-activeproperties, along with unusually low foaming properties.

The acid-sensitive, non-ionic, surface-active symmetrical formals ofthis invention may be represented by the formula in which R is an alkylgroup of 8 to 21 carbon atoms, and n is an integer of about 6 to 50. Rmay exhibit any of the known spatial configurations such as normal, iso,or tertiary. R may typically be octyl, nonyl, decyl, undecyl, dodecyl,tridecyl, pentadecyl, heptadecyl, octadecyl, nonadecyl or heneiscosyl.

The integer It varies from 6 to about 50. When n ranges from about 6 to12, the product is substantially oil soluble; and. when n ranges from 13to about 50, the product is substantially water soluble;

Patent ICC The present compounds are preferably prepared by reacting acompound having the formula 11 R COOHzX with one having the formula in amolecular ratio of substantially two of the former to one of the latter.The symbol X represents chlorine or bromine. The reaction is conductedin the presence of a strongly basic inorganic neutralizing agent. Amongthe basic agents that may be employed are the alkali metals, such assodium and potassium; the alkali metal hydroxides, such as sodiumhydroxide, potassium hydroxide, or lithium hydroxide; alkaline earthmetal hydroxides, such as barium hydroxide, calcium hydroxide, andstrontium hydroxide; alkali metal carbonates, such as sodium carbonate,potassium carbonate; and the like. The basic agent should be present inan amount somewhat greater than an equivalent amount of the halidereactant in order to assure the complete neutralization of thehydrochloric or hydrobromic acid formed in the reaction. It is possibleto react one molecular equivalent of the glycol with a molecularequivalent of each of two different halogenated reactants, if desired,in order to obtain different R groups on the hydrophobe ends of themolecule; but such usually leads to a mixture of prodncts.

The compounds of this invention are prepared by conducting the reactionin the temperature range of about l0 to 40 C., preferably 0 to 20 C. Thereaction is exothermic in nature. It is preferred to mix the alcohol andthe halogenated compound in a solvent and then add the basic agentgradually in small amounts. Suitable as a solvent in this respect arebenzene, toluene, xylene, and the like. Reaction time is not criticalbut generally Will vary from about thirty minutes to ten hours or more,depending largely on the individual reactants employed. While a solventis not required in this reaction, one is desirable in order to minimizethe effects of the exothermic nature of the reaction as previouslyindicated and also in order to aid in the separation of the inorganicsalt by-product formed.

Typical reactions that may be employed include:

CqHmC 0 011201 [I Cio nCOCHzBr 11 2: OOHaCl 13 210 0 CHaOl H sai O CHzCIO HHQQH? O CHzCl or any mixtures thereof, a

3 HO CH CH O H HO (CH CH O) H HO(CH CH O) H H (CH CH O) H HO (CH CH O HHO(CH CH O) H HO(CH CH O) H HO (CH CH O) H HO(CH CH O) H HO (CH CH O) Hand H0 CH CH O) H The reactants of this invention are known compounds orreadily prepared by known methods. In the preparation of the glycolreactants having 6m 50 ethoxy units, there is frequently obtained amixture of compounds having different numbers of ethoxy units. This isknown in the art and is no deterrent to the present reaction sincesatisfactory and useful compounds are formed from the mixtures ofcompounds in the same way as the individual compounds. It is to beunderstood, therefore, that the integer it stands for either the number.of. ethoxy units in a single compound or an average value in a mixtureof compounds. Likewise the compounds I ROCHtX are derived from fattyacids which are obtained frequently in commercial practice as mixtures.These mixtures lead to satisfactory and useful compounds.

At. the conclusion of the reaction, the halide salt formed as a reactionby-product is removed by filtration. The product is obtained as thefiltrate. If a solvent has been employed as indicated previously, it maybe removed by stripping. in a conventional manner. Even if a solvent hasnot been employed during the course of the reaction, the use of one isoften advantageous in the isolation of the product in order tofacilitate the removal of. the inorganic halide salt formed.

The. products of this invention, having the utilities previously stated,possess the hydrophobic-hydrophilic balance required for a substance toexhibit surface activi-- ty. As has been presented previously, it isfrequently. desirable to employ a surface-active material at one stageof aprocess and not have such material interfere at a later stage of theprocess as has been outlined heretofore. The present compounds may beused as valuable surface-active agents at one stage of a process andthen chemically altered to lose surface-activity at a later stage of theprocess. The present compounds are quite stable in alkaline or neutralmedia but may be chemically altered in an acidic media, particularly attemperatures approaching about 100 C. Hydrochloric acid or the like isparticularly convenient and eflfective for use in this respect; and thechange is efiected usually in a matter of minutes, such as or 10,depending largely on the temperatures and compounds involved. Thepresent compound is split into five fragments: two of which areformaldehyde; two are oily water-insoluble compounds, usually the same;and the fifth is a glycol. None of these fragments is surface'activc.Therefore, a compound is available that is surface-active during itsperiod of use when surface-activity is demanded and which can be readilyaltered to yield compounds that are no longer surface active and thatcan be readily disposed of when such conditions are required.

The compounds of this invention, as well as the methods for theirpreparation, may be more fully understood from the following exampleswhich are offered by way of illustration and not by way of limitation.Parts by weight are used throughout.

Example 1 There are introduced into-a reaction vessel 46 parts of H(OCHCH OH, 100 parts otberizene.and 50 parts of chloromethyl laurate. Themixture is cooled to 10 C. and eight parts of powdered potassiumhydroxide is added in small portions over a period of two hours. Thereaction mixture is held at 20 C., stirred at this temperature for twomore hours, and then filtered. The benzene is removed from the filtrateunder vacuum to yield parts of the bis ester,

ll N 01111230 0 CH2(0 2 9111 CH20 0 n aa In a similar manner there areprepared of H(OCH CH OH and parts of toluene. To this there is added. 62parts of chloromethylpalmitate.

The mixture is cooled to 0 C. and to it is added in small. portions.over a period of one hour five parts of powdered sodium hydroxide. Thetemperature is maintained at about 20 C. The reaction is allowed to cometo room temperature, stirred for one hour and finally filtered. Thesolvent is removed under vacuum to yield 220 parts of a light yellow waxwhich is soluble in water. This is identified.- as the his ester,

ll ll CmH C O CH2(OCzH O CHzO CCgsHar We claim:

1. A. composition of matter having the formula in which R is an alkylgroup of 8 to 21 carbon atoms and n is an integer of about 6 to 50.

2. A composition of matter having the formula 0 H II CnHzaC 0 CH2) 021100 OHQO C 0 11 3. A composition of matter having the formula II Ceilin 0CHKO (32119 0 01120 C 08H" 4. A composition of matter having the formulaII [I C nHasC O C HAO 0713.1) 220 01150 C C17H35 5'. A composition ofmatter having the formula H ll O11H23000HZ OC2HQ33OCH3OCO|1H23 6; Acomposition of matter having the formula ll ll 015 310 0 2( 2 0320 CHzOC Cns n References Cited in the file of this patent UNITED STATESPATENTS Gresham Feb. 19, 1946 De Benneville May 13, 1952 Cottle et al.June 18, 1957 FOREIGN PATENTS Germany Sept. 3, 1953 OTHER REFERENCESMcCutcheon, Synthetic Detergents, 1950, pp. 156-157.

1. A COMPOSITION OF MATTER HAVING THE FORMULA